CN106467583B - A kind of catalytic component, preparation method and application for vinyl polymerization - Google Patents
A kind of catalytic component, preparation method and application for vinyl polymerization Download PDFInfo
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- CN106467583B CN106467583B CN201510519047.3A CN201510519047A CN106467583B CN 106467583 B CN106467583 B CN 106467583B CN 201510519047 A CN201510519047 A CN 201510519047A CN 106467583 B CN106467583 B CN 106467583B
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Abstract
The present invention provides a kind of catalytic components for vinyl polymerization comprising chromium compound, organo-aluminum compound and the organoboron compound being supported on carrier, the organoboron compound contain B-R0B structure.The present invention also provides the preparation methods of the catalytic component, and the ethylene rolymerization catalyst based on the catalytic component, the catalyst has good polymerization activity, the polyethylene of available width molecular weight distribution for ethylene homo or ethylene and alpha-olefin copolymer.
Description
Technical field
The present invention relates to a kind of supported chrome series catalysts components, and the preparation method of the catalytic component is with it in ethylene
Application in polymerization.
Background technique
Ethene polymers is widely used as various products, and requires ethene polymers according to processing method and purpose
With different characteristics.For example, the polymer with lower molecular weight and Narrow Molecular Weight Distribution is suitable for passing through injection moulding film system
Product.On the other hand, the polymer with higher molecular weight and wide molecular weight distribution is suitable for through blow molding or aerated film system
The product of method film.In numerous applications to the polyethylene of high molecular weight in (such as pipe applications) needs, this quasi-polyethylene is answered
With enough intensity and good processing performance.
Chromium-based catalysts preparation can be used in ethene polymers with wide molecular weight distribution, and the chromium-based catalysts pass through
The chromium compound of load on an inorganic is calcined in non-reducing atmosphere makes its activation, and the chromium of fractional load is former
Son is converted into hexavalent chromium atoms acquisition.In the art, above-mentioned catalyst is commonly referred to as Phillips catalyst.Specific system
Preparation Method is that chromate is immersed on the carriers such as silica (silica gel), removes moisture and boils at a temperature of 400-1000 DEG C later
Dry and activation, the catalytic component being prepared is risen to store in dry air or in inert gas.This kind of catalytic component
Composition generally comprise carrier, active component and the co-catalyst that may be optionally added.Wherein carrier is inorganic oxide, active group
Be divided into the organic or inorganic compound of chromium, co-catalyst is metallo-organic compound, but each concrete component content of catalyst and
Preparation method is different, thus gained catalyst performance differ greatly (M.P.McDaniel, Adances in catalyst,
Volume 1985,33, the 47-98 pages).
The characteristics of chrome catalysts, is for chain growth and chain tra nsfer there is different activated centre ratios.This is urged
Agent is often generated short polymer chain and combines comonomer with short polymer chain with high-frequency, thus obtained polymerization
It there may be the comonomer and side chain of uneven distribution between each macromolecular of object.Therefore, manufactured polymer can be in width
Molecular weight distribution, thus there is good processing performance.But the catalyst also tends to, product melting long with induction time
The disadvantages of index is low, copolymerization performance is poor, hydrogen regulation performance is insensitive.In order to overcome these disadvantages of chrome catalysts, occur successively
The chromium-based catalysts of many modifications.Under normal circumstances, before preparation or in preparation process, some compounds are added, such as containing titanium,
The compound of the elements such as fluorine, aluminium, magnesium, zirconium is realized to the chemical modification of chrome catalysts or carrier, improves the catalysis of chromium-based catalysts
Performance.
For example, United States Patent (USP) US3887494 discloses a kind of preparation method of catalyst for olefinic polymerization, including will
Titanium compound is mixed with a kind of inorganic acid, and alkali silicate is added in the mixture and forms hydrogel, is about in pH value
Then aging hydrogel at 6.0,90 DEG C removes alkali metal with water, ammonium salt solution or Diluted Acid Washing, it is organic that a certain amount of water solubility is added
Compound separates organic matter and water from the mixture to form xerogel.Activation is dry solidifying containing chromium at 482-982 DEG C
Glue forms the catalyst for being used for olefinic polymerization.
1471431 A of Chinese patent CN discloses a kind of compound of the silicon oxide-containing of new magnesium processing, is suitable as chromium
The carrier of base olefin polymerization catalyst system, including by Mg (NO3)2.6H2O and Cr (NO3)3.9H2O contact generates composition, makes
Resulting composition is contacted with alkali to form magnesium hydroxide after it is dry.The introducing of magnesium increases the surface area of carrier in the catalyst,
The reduction of long chain branching in polyvinyl resin is resulted in, high molecular weight moieties are reduced, and polymer is in high molecular weight film application
With good impact property.
Chinese patent CN1745109 discloses a kind of catalyst system, is included in aluminum phosphate carrier and is loaded with chromium compound,
Then phosphorus/chromium molar ratio is handled and is roasted with the fluoride lower than 7wt% vehicle weight less than 0.3.Co-catalyst choosing
From Trialkylboron compounds, triarylboron, alkyl aluminum compound and combinations thereof.Using the catalyst copolymerization of ethylene of preparation
With 1- hexene, obtained copolymer can be not only used for manufacture minor diameter, it can also be used to manufacture the PE-100 pipe that diameter is more than 42 inches
Material is not in sagging or other gravity deformation phenomenons substantially.
The above-mentioned prior art is successively modified chromium-based catalysts using titanium, magnesium, phosphorus, fluorine, boron, makes the polymerization of catalyst
Activity, copolymerization performance, the molecular chain conformation of polymer and resin mechanical property obtained biggish improvement.But it is existing
Have there is no a kind of chromium-based catalysts system is disclosed in technology, there is good activity in the course of the polymerization process, and can obtain
The polymer of wide molecular weight distribution.
Summary of the invention
An object of the present invention is to provide a kind of catalytic component for vinyl polymerization, is catalyzed for supported chrome system
Agent component.
It is yet another object of the invention to provide the preparation methods of the catalytic component.
Another object of the present invention is to provide the ethylene rolymerization catalyst based on the catalytic component, is used for ethylene
Homopolymerization or ethylene and alpha-olefin copolymer have good polymerization activity, the adjustable molecular weight and molecule for obtaining polyvinyl resin
Amount distribution.
The catalytic component includes the chromium compound, organo-aluminum compound and organoboron compound being supported on carrier,
The organoboron compound contains B-R0B structure, wherein R0For C0-C30The saturation of linear chain or branched chain or unsaturated alkyl,
Halogenated alkyl or alkoxy, or be C3-C30Naphthenic base, or be C6-C30Aryl, alkaryl or aralkyl, Huo Zhewei
Heterocyclic substituent containing one or more N, O and S atom.Work as R0For C0Indicate that B-B key, i.e. two B are connected directly."R0For
C0-C30The meaning of the saturation of linear chain or branched chain or unsaturated alkyl, halogenated alkyl or alkoxy " is R0It can be not present,
It or is C0-C30Linear or branched alkyl group, or be C0-C30Saturation perhaps unsaturated alkyl or be C0-C30It is straight
Chain or branched haloalkyl, or be C0-C30Saturation perhaps unsaturated halogenated alkyl or be C0-C30Straight chain or branch
Chain alkoxy, or be C0-C30Saturation or unsaturated alkoxy.
According to the present invention, the structural formula of the organoboron compound is as shown in Formulas I or Formula II:
Wherein, R0For C0-C30The saturation of linear chain or branched chain perhaps unsaturated alkyl, halogenated alkyl or alkoxy or
For C3-C30Naphthenic base, or be C6-C30Aryl, alkaryl or aralkyl, or it is former to contain one or more N, O and S
The C of son4-C30Heterocyclic substituent.Preferably, R0For C0-C10The saturation of linear chain or branched chain or unsaturated alkyl, alkyl halide
Base or alkoxy, or be C3-C10Naphthenic base, or be C6-C20Aryl, alkaryl or aralkyl, or to contain one
The C of a or multiple N, O and S atom4-C20Heterocyclic substituent.
R1-R8And R1-R12Can be identical or different, it is each independently selected from hydrogen, halogen, C1-C20The saturation of linear chain or branched chain
Alkyl or halogenated alkyl, C2-C20Unsaturated alkyl or halogenated alkyl, the C of linear chain or branched chain3-C30Naphthenic base or halogenated cycloalkyl,
C6-C30Aryl or halogenated aryl, C7-C30Alkaryl or haloalkylaryl and C7-C30One in aralkyl or haloaralkyl
Kind.Preferably, R1-R8And R1-R12It is each independently selected from hydrogen, halogen, C1-C10The saturated alkyl or alkyl halide of linear chain or branched chain
Base, C2-C10Unsaturated alkyl or halogenated alkyl, the C of linear chain or branched chain3-C,10Naphthenic base or halogenated cycloalkyl, C6-C20Aryl or
Halogenated aryl, C7-C20Alkaryl or haloalkylaryl and C7-C20One of aralkyl or haloaralkyl.
Specific organoboron compound is selected from 4,4,4', 4', 5,5,5', two -1,3,2- dioxa of 5'- prestox -2,2'-
Ring pentaborane, 5,5,5', two -1,3,2- dioxa hexamethylene borine of 5'- tetramethyl -2,2'-, 4,4,4', 4', 6,6'- hexamethyl -
Bis- (2,3- dimethyl -2,3- butanediol) ethyl esters of bis- -1,3,2- dioxa hexamethylene borine of 2,2'-, 1- heptene -1,2- hypoboric acid,
(E) bis- (2,3- dimethyl -2,3- butanediol) ethyl esters of-A- styrene the hypoboric acid, (4,4,5,5- tetramethyl -1,3,2- of 4,4'- bis-
Dioxaborolanes -2- base) biphenyl, 4,4'- bis- (5,5- dimethyl -1,3,2- dioxa hexamethylene boron -2- base) biphenyl, 1,4-
Where are bis- (neopentyl glycol) esters of benzene hypoboric acid, 9,9- dimethyl fluorene -2,7- hypoboric acid pinacol ester, two frequency of anthracene -9,10- hypoboric acid
Bis- (methoxy methoxy the base) -1,1'- binaphthyl -3,3'- hypoboric acid frequencies of ester, (S)-(-) -2,2'- are which ester, tolans -4,4'- two
At least one of bis- (pinacol) esters of boric acid, the frequency of thiophene -2,5- hypoboric acid two any ester and boric acid three methylene ester.
In a specific embodiment of the present invention, the carrier is oxide carrier, and it typically is the porous nothings containing hydroxyl
Machine particle is preferred with spherical solid oxidic carrier.The optional self-alumina of the oxide carrier, silica, dioxy
Change one of titanium, boron oxide and zirconium oxide or their mixture, preferably silica, the silica gel in more preferable silica
As carrier, specific surface area 245-620m2/ g, Kong Rongwei 1.1-3.7cm3/g.Commercially available carrier can be directly used, carry
The content of body in the catalyst is 70-100wt%, preferably 90-99wt%.
In a specific embodiment of the present invention, the carrier will be dried before load, to remove free water.It is dry
Dry processing can carry out in air, in inert gas or under vacuum state.The temperature of drying process can be 100-600 DEG C,
Time is 1-10 hours.
In a specific embodiment of the present invention, the chromium compound is silane chromate ester, is preferably selected from bis- (triphenyl first silicon
Alkyl) chromate, bis- (trimethyl silyl) chromates, bis- (tribenzyl silicyl) chromates and bis- (triisopentyl first
At least one of silylation) compounds such as chromate.In these chromium compounds, most preferably with bis- (triphenylsilyls
Base) chromate.
In a specific embodiment of the present invention, the organo-aluminum compound general formula is Al (R ')m(OR”)nX(3-m-n), wherein
R ' and R " is identical or different, is each independently selected from hydrogen, halogen, C1-C20Alkyl, the C of linear chain or branched chain3-C20Naphthenic base, C6-
C20Aryl, C7-C20Alkaryl and C7-C20One of aralkyl, 0≤m≤3,0≤n≤3, and 1≤m+n≤3, wherein m and n
For integer, X is halogen.Specific organo-aluminum compound is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, one
Hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride, ethyoxyl diethyl
Aluminium, at least one of morpholine aluminium, methylaluminoxane, ethylaluminoxane and butyla-luminoxane are, it is preferable to use ethoxy
Base diethyl aluminum.
The present invention also provides the preparation methods of the catalytic component, including chromium compound is supported on carrier, so
Organo-aluminum compound and organoboron compound are added afterwards.
Further, preparation method of the present invention for the catalytic component of vinyl polymerization, comprising the following steps:
(1) chromium compound is dissolved in organic solvent, carrier is added and obtains mixture；
(2) organo-aluminum compound and organoboron compound are added in the mixture that step (1) obtains, after being stirred
Solvent is removed, the catalytic component is obtained.
In a specific embodiment of the present invention, carrier described in step (1) is previously dried processing, preferably in 100-
It is carrier 1-10 hours dry at 600 DEG C；The organic solvent is C4-C20Alkane；The weight ratio of carrier and chromium is (10-1000):
1。
In a specific embodiment of the present invention, organoboron compound first can be added again added with machine aluminium compound in step (2),
First organoboron compound can also be added to be added simultaneously again added with machine aluminium compound, or by organo-aluminium and organoboron compound.Aluminium
It is (1-100) with the molar ratio of chromium: 10, the molar ratio of boron and chromium is (1-100): 10.
Chromium compound described in preferred steps (2) is bis- (triphenyl-silyl) chromates, organic described in step (3)
Aluminium compound is diethylaluminum ethoxide.
The present invention also provides a kind of catalyst for vinyl polymerization, including following component:
(1) catalytic component of the present invention for vinyl polymerization；
(2) co-catalyst, be in the periodic table of elements first, second and third or four main group or the second transition group metallic element
The organo-metallic compound of formation.
In a specific embodiment of the present invention, the co-catalyst be selected from substituted or unsubstituted alkyl metal cpd or
Alkoxide compound, the substituted or unsubstituted alkyl metal cpd are selected from n-BuLi, boron triethyl, trimethyl
Aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine
At least one of diisobutyl aluminum, ethyl aluminum dichloride and diethyl zinc, the alkoxide compound are preferably alkoxide
C1-C10Alkyl aluminum, such as diethylaluminium ethoxide, morpholine aluminium.In addition methylaluminoxane, ethyl also can be used
Aikyiaiurnirsoxan beta or butyla-luminoxane etc., the preferably described co-catalyst are triethyl aluminum.
In a specific embodiment of the present invention, the molar ratio of the co-catalyst and chromium is (0.1-100): 1, preferably
(0.5-50):1。
Catalyst of the present invention can be used for ethylene homo, can be used for ethylene and other olefin-copolymerizations.It is described
Other alkene can be selected from C3-C20Alpha-olefin, aromatic vinyl compound, one in alicyclic ring vinyl compound and cycloolefin
Kind is several.Such as propylene, butylene, hexene, 3-methyl-1-butene, 3- ethyl -1- amylene, styrene, allyl benzene, vinyl
Hexamethylene, vinyl cyclopentane, cyclohexene, norbornene, 5- methyl -2- norbornene etc..
The present invention is suitable for using known device and any polymerization technique by slurry, solution or gas phase process,
And it is not limited to any certain types of polymerization system.
When the present invention is used for slurry polymerization processes, a kind of inertia alkane is typically chosen as diluent, makes polymer particles
Grain can be discrete in diluent in from of a slurry, after reaction by flashing or being filtered to remove diluent.Common diluent
There are propane, iso-butane, pentane, hexane, heptane etc..Typical polymerizing condition is polymerization temperature at 20-250 DEG C, preferably in 50-
160℃；The pressure of polymerization is in 1-100atm, preferably in 5-80atm.The molten of modifying polymerization with hydrogen object can be used in polymerization process
Melt index and molecular weight.
When the present invention is used for stirring or fluidized bed gas-phase polymerization technique, reaction pressure is in 3-30atm, preferably 6-
25atm；Temperature is at 30-150 DEG C, and preferably 70-120 DEG C.Under normal circumstances, under the appropriate reaction conditions, starting monomer is kept
Flow velocity so that the granular bed in reactor is in suspended state, polyethylene product is continuously discharged out of reactor.It polymerize
The molecular weight and molecualr weight distribution that oxygen adjusts polymer can be added in journey.Present invention is particularly suitable for stirring or fluidized beds
Gas-phase polymerization system.
When the catalytic component is used for gas-phase polymerization, organo-aluminum compound, organoboron compound and silane chromate ester
Collective effect shorten the induction period in polymerization of chromium-based catalysts, improve the activity of chromium-based catalysts.With catalysis of the invention
The molecular weight ethylene polymer distribution (Mw/Mn) of agent component production is can be controlled between 5-100, and density can be controlled in 0.945-
0.965g/cm3Between.
Detailed description of the invention
Fig. 1 is that the catalyst gas-phase polymerization of embodiment evaluates kinetic curve.
Specific embodiment
Following embodiment is provided so that the present invention is better described, the range being not intended to limit the invention.
Test method:
1, polymer molecular weight is distributed (Mw/Mn): it is seeped with Polymer Labo ratories company PL-GPC220 type gel
Average weight-molecular mass (the M of saturating chromatography (GPC) measurement polymerw), the equal relative molecular mass (M of numbern) and its distribution (Mw/
Mn)。
2, it density: is measured according to ASTM D-1505.
3, ethylene polymerization activity: with every gram of catalyst per hour gained resin weight indicate.
The preparation of catalytic component
Embodiment 1
Taking 10g silica gel, (W.R.Grece&Co.-Com 955, pore volume are about 1.1-1.8cm3/ g, surface area are about 245-
375m2/ g) 200 DEG C drying 4 hours under nitrogen fluidisation.It is added into the reactor being sufficiently displaced from the nitrogen of anhydrous and oxygen-free
Bis- (triphenyl-silyl) chromates of 0.5g, then be added 300ml hexane, be stirred at room temperature make solid be completely dissolved to be formed it is molten
Liquid.10g silica gel after drying is added in above-mentioned solution, oneself of 2ml (1.3M) diethylaluminum ethoxide is first added after stirring
Alkane solution after being stirred at room temperature 1 hour, adds 4,4'- bis- (4,4,5,5- tetramethyls -1,3, the 2- dioxane penta of 2.4mmol
Borine -2- base) biphenyl, solvent is removed after being stirred at room temperature 1 hour, obtains the catalytic component containing chromium.The polymerization evaluation of catalyst
As a result it is listed in table 1.
Embodiment 2
Taking 10g silica gel, (W.R.Grece&Co.-Com 955, pore volume are about 1.1-1.8cm3/ g, surface area are about 245-
375m2/ g) 200 DEG C drying 4 hours under nitrogen fluidisation.It is added into the reactor being sufficiently displaced from the nitrogen of anhydrous and oxygen-free
Bis- (triphenyl-silyl) chromates of 0.5g, then be added 300ml hexane, be stirred at room temperature make solid be completely dissolved to be formed it is molten
Liquid.10g silica gel after drying is added in above-mentioned solution, 4, the 4'- bis- (4,4,5,5- tetra- of 2.4mmol is first added after stirring
Methyl-1,3,2- dioxaborolanes -2- bases) biphenyl, after being stirred at room temperature 1 hour, add 2ml (1.3M) diethyl ethoxy
The hexane solution of base aluminium after being stirred at room temperature 1 hour, removes solvent and obtains the catalytic component containing chromium.The polymerization evaluation of catalyst
As a result it is listed in table 1.
Embodiment 3
Taking 10g silica gel, (W.R.Grece&Co.-Com 955, pore volume are about 1.1-1.8cm3/ g, surface area are about 245-
375m2/ g) 200 DEG C drying 4 hours under nitrogen fluidisation.It is added into the reactor being sufficiently displaced from the nitrogen of anhydrous and oxygen-free
Bis- (triphenyl-silyl) chromates of 0.5g, then be added 300ml hexane, be stirred at room temperature make solid be completely dissolved to be formed it is molten
Liquid.10g silica gel after drying is added in above-mentioned solution, 2ml (1.3M) diethylaluminum ethoxide is added after stirring simultaneously
4,4'- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborolanes -2- base) biphenyl of hexane solution and 2.4mmol, room temperature
Stirring removed solvent after 2 hours, obtained the catalytic component containing chromium.The polymerization evaluation result of catalyst is listed in table 1.
Embodiment 4
Except 4,4'- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2- base) biphenyl is changed to 5,5,5', 5'-
Tetramethyl -2,2'- bis- -1, other than 3,2- dioxa hexamethylene borines, the preparation method is the same as that of Example 1 for catalytic component.
Embodiment 5
Except 4,4'- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2- base) biphenyl is changed to 9,9- dimethyl
Other than fluorenes -2,7- hypoboric acid pinacol ester, the preparation method is the same as that of Example 1 for catalytic component.
Embodiment 6
Except 4,4'- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2- base) biphenyl is changed to three methylene of boric acid
Other than ester, the preparation method is the same as that of Example 1 for catalytic component.
Comparative example 1
Taking 10g silica gel, (W.R.Grece&Co.-Com 955, pore volume are about 1.1-1.8cm3/ g, surface area are about 245-
375m2/ g) 200 DEG C drying 4 hours under nitrogen fluidisation.It is added into the reactor being sufficiently displaced from the nitrogen of anhydrous and oxygen-free
Bis- (triphenyl-silyl) chromates of 0.5g, then be added 300ml hexane, be stirred at room temperature make solid be completely dissolved to be formed it is molten
Liquid.10g silica gel after drying is added in above-mentioned solution, the hexane of 2ml (1.3M) diethylaluminum ethoxide is added after stirring
Solution removes solvent after being stirred at room temperature, and obtains the catalytic component containing chromium.The polymerization evaluation result of catalyst is listed in table 1.
Comparative example 2
Except 4,4'- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2- base) biphenyl be changed to boron triethyl with
Outside, the preparation method is the same as that of Example 1 for catalytic component.
Vinyl polymerization:
Slurry polymerization
Polymerization reaction carries out in one 1 liter of autoclave, and the speed of stirring is 450rmp, and reaction kettle is equipped with stainless
Steel clamp set, the liquid medium in collet can accurately control reaction temperature.After reaction kettle is vacuumized and is replaced three times with ethylene,
Pressure is slightly above the purifying hexane of addition 500ml under conditions of 0.1MPa in holding kettle, and 0.5ml (1M) triethyl aluminum is then added
The temperature of reaction system is raised to 80 DEG C by the ingredient of solid catalyst of solution and 400mg, and being finally passed through ethylene makes pressure in kettle
Reach 1.1MPa, is kept for stagnation pressure one hour of constant reaction.After polymerization, stopping is passed through ethylene, after the slow release of reaction kettle,
Polyethylene is separated from hexane, is weighed after being finally dried.The polymerization activity production of catalyst per hour per gram
Polymer total amount indicates (gPE/gCat.hr).
Gas-phase polymerization
Polymerization reaction carries out in one 1 liter of autoclave, and the speed of stirring is 300rmp, and reaction kettle is equipped with stainless
Steel clamp set, the liquid medium in collet can accurately control reaction temperature.Reaction kettle is vacuumized with after ethylene displacement three times, is being protected
It holds pressure in kettle and is slightly above under conditions of 0.1MPa and processed 955 silica gel of Grace Davison of 15g is added (silica gel is logical
It crosses at 600 DEG C and is dehydrated, triethyl aluminium solution then is added according to the ratio of every gram of silica gel 0.6mmol aluminium, finally removes solvent
The step of obtain.The decentralized medium for functioning as catalyst in gas-phase polymerization of silica gel is added, is conducive to activated centre performance
Effect).Then the ingredient of solid catalyst of 300mg is added, the temperature of reaction system is raised to 100 DEG C.Finally being passed through ethylene makes
Pressure in kettle reaches 1.1MPa, is kept for stagnation pressure one hour of constant reaction.After polymerization, stopping is passed through ethylene, reaction kettle
Kettle temperature is down to room temperature after slow release, and polyethylene is separated from silica gel, is weighed after being finally dried.Polymerization activity is used
The polymer total amount of catalyst production indicates per hour per gram, unit gPE/gCat.hr.
By above-mentioned polymerization process, the ingredient of solid catalyst in embodiment and comparative example is respectively used to vinyl polymerization, is gathered
It closes result and is listed in table 1 and Fig. 1.
1 catalyst slurry polymerization evaluation result of table
From table 1 it follows that introducing organoboron compound in catalyst preparation process, silane chromate ester catalysis is improved
The polymerization activity of agent, the polyvinyl resin molecular weight distribution of preparation broaden (Mw/Mn), the melt strength of resin improves, and is blow molded performance
It is improved with processing stability, is particularly conducive to blow molding and prepares Large Hollow Container.It simultaneously can be in the base for stablizing processing
Ultrathin film is blown on plinth, and the tear resistance for the film blown is more preferable.
Ethene gas-phase polymerization evaluation is carried out respectively to the catalytic component of embodiment 1, comparative example 1 and comparative example 2, polymerization is dynamic
Mechanics result is listed in Fig. 1.It can be seen from the figure that the catalyst of comparative example 1 is used to longer polymerization occur when gas-phase polymerization
The polymerization activity of induction period, catalyst are slower in incipient stage growth, and subsequent activity is held essentially constant.Embodiment 1 and implementation
In gas-phase polymerization processes, induction period is obviously shortened the catalyst of example 2, higher activity is just presented in the incipient stage, then fastly
Speed decaying, subsequent activity are basically unchanged or slowly decline.Illustrate in gas-phase polymerization processes, joined the silicon of organoboron compound
Alkane chromate ester catalyst shortens induction period in polymerization, improves the activity of chromium-based catalysts.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (16)
1. a kind of catalytic component for vinyl polymerization, including be supported on carrier chromium compound, organo-aluminum compound and
Organoboron compound, the chromium compound are silane chromate ester；The organoboron compound contains B-R0B structure, wherein R0For
C0-C30The saturation of linear chain or branched chain or unsaturated alkylidene, halogenated C0-C30The saturation or unsaturation of linear chain or branched chain
Alkylidene, C0-C30The saturation of linear chain or branched chain or unsaturated alkylene oxide group, C3-C30Cycloalkylidene, C6-C30Asia
Aryl, C7-C30Alkarylene, C7-C30Sub- aralkyl or C containing one or more N, O and S atom4-C30Asia
Heterocyclic substituent, the structural formula of the organoboron compound is as shown in Formulas I or Formula II:
Wherein, R1-R8And R1-R12It is identical or different, it is each independently selected from hydrogen, halogen, C1-C20The saturation alkane of linear chain or branched chain
Base, halogenated C1-C20Saturated alkyl, the C of linear chain or branched chain2-C20The unsaturated alkyl of linear chain or branched chain, halogenated C2-C20Directly
The unsaturated alkyl of chain or branch, C3-C30Naphthenic base, halogenated C3-C30Naphthenic base, C6-C30Aryl, halogenated C6-C30Aryl,
C7-C30Alkaryl, halogenated C7-C30Alkaryl, C7-C30Aralkyl and halogenated C7-C30One of aralkyl.
2. catalytic component according to claim 1, which is characterized in that the organoboron compound is selected from 4,4,4', 4',
Two -1,3,2- dioxaborolanes of 5,5,5', 5'- prestox -2,2'-, 5,5,5', two -1,3,2- of 5'- tetramethyl -2,2'-
Dioxa hexamethylene borine, 4,4,4', two -1,3,2- dioxa hexamethylene borine of 4', 6,6'- hexamethyl -2,2'-, 1- heptene -1,2-
Bis- (2,3- dimethyl -2,3- butanediol) ethyl esters of hypoboric acid, the bis- (2,3- dimethyl -2,3- fourths two of (E)-A- styrene hypoboric acid
Alcohol) ethyl ester, 4,4'- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2- base) biphenyl, the bis- (5,5- bis- of 4,4'-
Methyl-1,3,2- dioxa hexamethylene boron -2- base) biphenyl, bis- (neopentyl glycol) esters of 1,4- benzene hypoboric acid, dimethyl fluorene -2 9,9-,
7- hypoboric acid pinacol ester, the frequency of anthracene -9,10- hypoboric acid two which ester, bis- (methoxy methoxy the base) -1,1'- dinaphthalenes of (S)-(-) -2,2'-
Base -3,3'- hypoboric acid frequency any ester, bis- (pinacol) esters of tolans -4,4'- hypoboric acid, two frequency of thiophene -2,5- hypoboric acid where ester
At least one of with three methylene ester of boric acid.
3. catalytic component according to claim 1 or 2, which is characterized in that the carrier is oxide carrier.
4. catalytic component according to claim 3, which is characterized in that the carrier is selected from aluminium oxide, silica, two
At least one of titanium oxide, boron oxide and zirconium oxide.
5. catalytic component according to claim 4, which is characterized in that the carrier is silica.
6. catalytic component according to claim 5, which is characterized in that the carrier is silica gel.
7. catalytic component according to claim 1 or 2, which is characterized in that the chromium compound is selected from bis- (triphenyl first
Silylation) chromate, bis- (trimethyl silyl) chromates, bis- (tribenzyl silicyl) chromates and bis- (triisopentyls
At least one of silicyl) compounds such as chromate.
8. catalytic component according to claim 7, which is characterized in that the chromium compound is bis- (triphenylsilyls
Base) chromate.
9. catalytic component according to claim 1 or 2, which is characterized in that the organo-aluminum compound general formula is Al
(R’)m(OR”)nX(3-m-n), wherein R ' and R " is identical or different, is each independently selected from hydrogen, halogen, C1-C20Linear chain or branched chain
Alkyl, C3-C20Naphthenic base, C6-C20Aryl, C7-C20Alkaryl and C7-C20One of aralkyl, 0≤m≤3,0≤n≤3,
And 1≤m+n≤3, wherein m and n is integer, and X is halogen.
10. catalytic component according to claim 9, which is characterized in that the organo-aluminum compound be selected from trimethyl aluminium,
Triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine two
Aluminium isobutyl, ethyl aluminum dichloride, diethylaluminium ethoxide, morpholine aluminium, methylaluminoxane, ethylaluminoxane and butyl
At least one of aikyiaiurnirsoxan beta.
11. catalytic component according to claim 10, which is characterized in that the organo-aluminum compound is ethyoxyl diethyl
Base aluminium.
12. the preparation method of catalytic component according to any one of claim 1 to 11, comprising:
(1) chromium compound is dissolved in organic solvent, carrier is added and obtains mixture；
(2) organo-aluminum compound and organoboron compound are added in the mixture that step (1) obtains, are removed after being stirred
Solvent obtains the catalytic component.
13. according to the method for claim 12, which is characterized in that carrier described in step (1) is previously dried processing；
And/or
The organic solvent is C4-C20Alkane.
14. a kind of catalyst for vinyl polymerization, comprising:
(1) catalytic component described in any one of claims 1 to 11；
(2) co-catalyst, in the periodic table of elements first, second and third or four the metallic element of main group or the second transition group formed
Organo-metallic compound.
15. catalyst according to claim 14, which is characterized in that the co-catalyst is triethyl aluminum.
16. catalyst described in catalytic component described in any one of claims 1 to 11 or claims 14 or 15 is in second
Application in polyamino alkenyl or ethylene and other olefin-copolymerizations.
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| CN108690151B (en) * | 2017-04-07 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and olefin polymerization method |
| CN116251728B (en) * | 2023-01-03 | 2023-09-19 | 万华化学集团股份有限公司 | Method for reducing polymer adhesion in ethylene oligomerization reactor |
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| WO2001025244A1 (en) * | 1999-10-06 | 2001-04-12 | Sri International | Complexes of mid-transition metals and unsaturated nitrogenous ligands as single-site catalysts |
| CN102388071A (en) * | 2009-04-10 | 2012-03-21 | 沙特基础工业公司 | Process for the production of an ethylene polymer using a chromium containing catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001025244A1 (en) * | 1999-10-06 | 2001-04-12 | Sri International | Complexes of mid-transition metals and unsaturated nitrogenous ligands as single-site catalysts |
| CN102388071A (en) * | 2009-04-10 | 2012-03-21 | 沙特基础工业公司 | Process for the production of an ethylene polymer using a chromium containing catalyst |
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